Synthesis And Properties Of Asymmetric Porphyrins And Their Anthraquinone Derivatives

Porphyrin derivatives, due to their exclusive optical properties, play a significant role in the research of photoelectric materials. Meanwhile, porphyrins and their relatives are the cores of chlorophyll molecules. As the primary electron donor, they participate in a series of important processes in photosynthesis. So porphyrins are important compounds in artificial photosynthesis to imitate the electron and energy tranfer in nature photosynthesis.Hydroxyl and amino are functional groups and nitro-substituted aromatic compounds have been found to be effective electron-affinity radio sensitizers. Furthermore, porphyrins bearing hydroxyl, nitro and amino groups are useful synthetic precursors to active molecules, so it is important to study the synthesis of porphyrins bearing these groups.In the thesis, several unsymmetrical porphyrins bearing hydroxyl group and their Mn complexes were synthesized by Adler method; two porphyrins bearing nitro group were synthesized by nitration of TPP and Adler method; porphyrins bearing amino group were synthesized by the reduction of nitroporphyrins and the optimal process conditions was ensured. Those compounds were characterized by IR, 1H NMR and MS.Quinone compounds are the primary electron acceptor in nature photosynthesis, thus building model compounds of artificial photosynthesis with quinone as acceptor is the first selection to the scholar. In the dissertation, model compounds were built with porphyrin (P) as electron donor and anthraquinone (AQ) as acceptor. 5 novel porphyrin-anthraquinone dyads were designed and synthesized based on the synthesis of a series of asymmetry porphyrins. They respectively connected with azo bond and with alkyl chain as bridge. The compounds were characterized by IR, 1H NMR and MS.Porphyrin-bipyridine dyad 9d was prepared from amino porphyrin and 4-dimethyl-4'-carboxylchlroride-2, 2'-bipyridine. It was prepared to make foundation for the further synthesis of porphyrin-bipyridine-Mn model compounds.The absorption properties, fluorescence spectra, transient absorption spectroscopy and oxidation-reduction potential of the compounds above were studied and compared with TPP. The results exhibit that the introduction of naphthyl and 3, 4-methylenedioxy phenyl group can enhance the conjugate degree of porphyrins and cause red-shift of the absorption spectra. In the porphyrin-anthraquinone molecule, the fluorescence quenching was observed due to the photoinduced intramolecular electron transfer from the excited porphyrin singlet state to the appended anthraquinone.